JPH027360B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for producing ultra-concentrated powder detergent,
More specifically, the present invention relates to a method for producing an ultra-concentrated powder detergent with high free-flowing properties that contains an anionic surfactant at a high density and concentration. Conventionally, powdered detergents based on anionic surfactants have been made by adding inorganic builders such as zeolite, sodium tripolyphosphate, sodium carbonate, sodium silicate, and Glauber's salt to an aqueous solution of anionic surfactants, carboxyl groups, and/or hydroxyl groups. It is manufactured by spray drying a slurry containing a high molecular weight organic polymer, etc. The spray drying method has advantages such as high productivity, uniform distribution of ingredients in the product, and uniform particle size, but on the other hand, the bulk specific gravity of the product is low;
It also has drawbacks such as consuming a large amount of energy to evaporate a large amount of water. In recent years, with the emphasis on saving resources and energy, the bulkiness of detergents has become a problem in terms of transportation and for housewives to carry them. From the perspective of energy saving, several methods have been proposed for producing detergents containing anionic surfactants that do not require spray drying. For example, Japanese Patent Publication No. 52-30962 discloses a method for producing a heavy powder detergent in which fatty acids are neutralized with water-containing powdered soda carbonate at a temperature above the melting point. However, this method requires heating, the resulting detergent has insufficient solubility, and is soap-based, resulting in poor cleaning power. Also, US Patent No. 3,434,974 specifies
Discloses a method of neutralizing alkylbenzenesulfonic acid with sodium bicarbonate, sodium tripolyphosphate, etc. However, because this method uses sodium bicarbonate and contains a relatively large amount of water, the detergent that can be obtained is limited to rod-shaped detergents. Further, US Pat. No. 3,597,361 discloses a method in which a concentrated solution of alkylbenzene sulfonic acid and sodium hydroxide is sprayed into a rotating drum containing a powder containing sodium tripolyphosphate as a builder. However, this method has a major drawback in that zeolite cannot be used as a builder. Therefore, based on the above technical issues, the present inventors aimed to obtain an energy-saving ultra-concentrated powder detergent with high free-flowing properties that contains anionic surfactants at high density and concentration. As a result of intensive research, the present invention was completed. That is, the present invention provides unneutralized sulfonated products and/or sulfated products (hereinafter referred to as unneutralized products),
Neutralize and mix with 2 to 10 mol of sodium carbonate and 1 to 10 mol of water per 1 mol of the unneutralized substance in a strong shearing device such as a kneader, and after cooling to 40°C or less,
The present invention provides a method for producing an ultra-concentrated powder detergent, which is characterized by pulverizing or crushing and granulating the detergent together with powdered zeolite and other detergent formulations. The unneutralized sulfonated or sulfated product used in the present invention refers to straight-chain or branched alkylbenzene sulfonic acid having an alkyl group having an average of 10 to 16 carbon atoms, and an alkyl benzene sulfonic acid having an alkyl group having an average of 10 to 18 carbon atoms. It has a sulfate ester and an alkenyl group, and 1
It is an alkenyl ether sulfate ester with an average of 0.5 to 8 moles of ethylene oxide or a mixed alkylene oxide of ethylene oxide and propylene oxide or butylene oxide added to the molecule. In carrying out the present invention, a combination system of a linear or branched alkylbenzenesulfonic acid and an alkyl sulfate ester satisfies production costs and cleanability, while providing excellent crushing and granulation properties in the subsequent process. This is preferable in this respect. Further, in practice, a combination in which one of the two is unneutralized may also be used, such as a combination of sodium alkyl sulfate and unneutralized alkylbenzenesulfonic acid. The sodium carbonate used in the present invention can be either dense ash (apparent specific gravity 1.0) or light ash (apparent specific gravity 0.6), but since the reaction occurs from the surface of sodium carbonate, light ash with a large specific surface area The reactivity is better. It is also possible to use a pulverized product of sodium carbonate, which also provides better reactivity. Furthermore, as the sodium carbonate used in the present invention, anhydrous or monohydrate can be used. If the amount of sodium carbonate is less than 2 moles per 1 mole of unneutralized material, the reactivity will be low and the reaction will take a long time, and a large amount will remain unneutralized until the subsequent process, which will have a negative impact on the powder properties of the product. . Moreover, if the amount of sodium carbonate is 10 moles or more, the effect on the reactivity remains the same, and this is not preferable from an economic standpoint or the purpose of concentration. Moisture is introduced from other ingredients added during neutralization and from the water in the sodium carbonate and the water in the unneutralized product. It is also possible to add only water. Other ingredients added during neutralization are sodium hydroxide aqueous solution, sodium silicate and its aqueous solution,
These include high molecular weight organic polymers containing carboxyl groups and/or hydroxyl groups and aqueous solutions thereof, polyalkylene glycols and aqueous solutions thereof, perfumes and aqueous solutions thereof, fluorescent dyes and aqueous solutions thereof, pigments and aqueous solutions thereof, and the like. Some of these components that can be introduced have the effect of promoting the neutralization reaction. For example, addition of a small amount of aqueous sodium hydroxide solution and aqueous sodium silicate solution accelerates the neutralization reaction and also contributes to the reaction with unneutralized substances as an alkaline component.
As the sodium silicate, various sodium salts of silicic acid, such as sodium metasilicate and its hydrates in various proportions, sodium orthosilicate, etc. can be used, and water glass can also be used. In addition, high molecular weight organic polymers and aqueous solutions containing carboxyl groups and/or hydroxyl groups are effective as detergent ingredients, and usually have a molecular weight of 500 to 100,000.
are used. By introducing these components at the time of neutralization and mixing, the detergent can have an appropriate hardness, and may also have an effective effect on crushing and granulation in the subsequent process. Suitable compounds as high molecular weight organic polymers containing carboxyl and/or hydroxyl groups include polymers and copolymers of acrylic acid, hydroxyacrylic acid, maleic acid, itaconic acid, mesaconic acid, aconitic acid and the like. and polyvinyl alcohol. Examples of the polyalkylene glycol include polyethylene glycol and polypropylene glycol. In the present invention, if the amount of water is less than 1 mol relative to the unneutralized product, the neutralization reaction will be slow and a long residence time will be required to complete the reaction, which is impractical. On the other hand, it is inappropriate to introduce 10 moles or more of water relative to the unneutralized product, since this poses a problem in the stickiness of the resulting neutralized product and also makes it impossible to smoothly perform crushing and granulation in the subsequent step. The amount of water is preferably 1 to 5 moles per mole of unneutralized material. The devices used for the neutralization reaction in the present invention are strong shearing devices such as kneaders, such as the Honda Container Kneader (Honda Iron Works Co., Ltd.) and the Multibar Pass Continuous Mixer (BAKER).
PERKINS INC.), KRC Kneader (Kurimoto Iron Works)
Co., Ltd.), Nesco Kneader (Fuji Sangyo Co., Ltd.), etc. The above-mentioned kneading machines all have a mechanism that increases the chance of contact between the unneutralized material and sodium carbonate, and are characterized by having a continuous self-cleaning mechanism. A residence time of about 1 minute in these devices is usually sufficient. Although the neutralization reaction is initiated within these devices having a self-cleaning mechanism, it is sufficient that the neutralization reaction is completed by the time the reactants are discharged from the device, cooled, and transferred to the pulverization process. The degree of neutralization can also be checked by adding an indicator such as methyl orange or methyl red in advance during mixing and neutralization. The temperature of the neutralized product when discharged from these kneaders is 40° to 100°C. Normally, when processing with a single-stage kneader, 30% to 80% of the unneutralized material is neutralized. Since the neutralization reaction mainly takes place via the particle surface of sodium carbonate, it is important to renew the interface as much as possible. The neutralized product discharged from the kneader is cooled to 40° C. or lower by cooling in a fluidized bed, a belt type cooler, stirring cooling, or the like. Upon cooling, the neutralization reaction is completed. The cooled neutralized product is first crushed or crushed into chunks. Powdered zeolite and other detergent formulations are then added and ground. Usually crushed to 1500μ or less, preferably 800μ or less. The crusher is Huitumil (Hosokawa Micron Co., Ltd.),
Paraplex (Fuji Sangyo Co., Ltd.), rotary cutter mill (Nara Kikai Co., Ltd.), etc. are suitable. After crushing, it is classified through a sieve, and the coarse particles are mixed with powdered zeolite again and crushed and granulated. By crushing and granulating, a detergent powder with excellent fluidity can be obtained.
The amount of powdered zeolite is determined depending on the amount added to the final product, and is usually 10 to 40% by weight. A detergent composition is obtained by mixing the crushed and granulated detergent powder with other detergent formulations. Other detergent formulations include nonionic surfactants, foam stabilizers, fabric softeners, bleaches, enzymes, fluorescent dyes, and fragrances. Mixing can be carried out using a Schugi Mixer, a L¨odige Mixer, a Patterson-Cary Blender, or the like. In order to impart fluidity and smoothness to the granulated detergent obtained by mixing, it is also possible to add a fluidity-improving additive such as powdered zeolite. The detergent thus obtained has a dissolution rate comparable to powdered detergents produced by conventional spray drying;
In addition, the caking properties are better than conventional products,
Together with its high anionic active agent content and high apparent density, it has extremely excellent properties when used, which is why it is called an "ultra-concentrated detergent." EXAMPLES The present invention will be specifically described below with reference to Examples, but the present invention is not limited to these Examples. Example 1 FM-NES-120 type Nesco kneader (Fuji Sangyo)
Ltd. was supplied with a fixed amount of raw materials having the following composition. Straight chain alkylbenzenesulfonic acid (average carbon number of alkyl group C = 12) (acid value 187, moisture 0.7%,
Free sulfuric acid 3%) 48Kg/Hr Alkyl sulfate ester (=12.5) 15Kg/Hr Anhydrous light ash (manufactured by Toyo Soda Co., Ltd.) 60Kg/Hr 48% sodium hydroxide aqueous solution 4Kg/Hr Sodium silicate aqueous solution (No. 2 SiO ₂ /Na ₂ O molar ratio = 2.5) 5Kg/Hr The reactant was discharged from the Nesco kneader at about 70℃, kneaded in an extruder, formed into a size of about 8 mm square, and heated at 30℃ in a fluidized bed. The following composition was obtained.

[Table] The average residence time in the Nesco kneader was about 2 minutes. Further, the alkyl sulfate was used in the experiment of this example immediately after being sulfated by a known method, and the temperature was about 40°C. Other ingredients are kept at room temperature. To 80 parts of this composition, 20 parts of powdered zeolite (Toyo Builder powder product manufactured by Toyo Soda Co., Ltd.) was added and mixed, and the mixture was ground to 1000 μm or less using a hammer mill. Enzyme,
Added fluorescent dye, nonionic surfactant, and fragrance.
Then 5% powdered zeolite was added. Mixing was done in a Shuyugi mixer. The obtained powder detergent had an apparent specific gravity of 0.75 g/cc. The obtained powder detergent was evaluated for detergency, foaming power, foam stability, solubility, caking property, etc. The evaluation results are shown in Table 1.
(25% by weight), the cleaning performance based on the amount of active agent used was the same, and the other powder physical properties were also the same. Example 2 The following components were separately fed in fixed amounts into the same apparatus as in Example 1. Linear alkylbenzenesulfonic acid 50Kg/Hr Alkyl sulfate ester salt 24 〃 Anhydrous light ash (manufactured by Toyo Soda Co., Ltd.) 50 〃 Anhydrous sodium metasilicate 10Kg/Hr Polyethylene glycol aqueous solution (average molecular weight
10000, effective content 70%, moisture 30% 5 The above composition obtained from the Nesco kneader at about 60°C is cooled to about 35°C on a cooling belt (Sandvik steel belt), and then the above reactant is cooled to about 35°C.
90 parts and 10 parts of powdered zeolite were mixed and pulverized using a Huitumill (manufactured by Hosokawa Micron Co., Ltd.) until the particle size was 1000 μm or less. After pulverization, other detergent formulations were added and granulated to obtain a highly fluid detergent powder with an average particle size of about 500μ. The apparent specific gravity was 0.78 g/cc. Table 1 shows the evaluation results of the obtained powder detergent.
The evaluation method for detergents in Table 1 is as follows. Detergent power was measured according to the JIS method using a commercially available detergent as a standard and using the Sietshue paired comparison method. + Superiority at 5% risk level ± Equal to - Inferior Foaming power Pour 30 liters of tap water at 20℃ into a commercially available electric washing machine.
Add and dissolve 20 g of detergent (40 g of control commercial detergent). 1 kg of cotton underwear and artificial oily dirt (cottonseed oil) were added, and the foaming state was determined after 10 minutes of strong inversion. Solubility: Keep ion-exchanged water 1 at 10℃ and stir gently with a magnetic stirrer.
Add 1.33g. After 5 minutes, the detergent solution was passed through a 200 mesh sieve and the residue on the sieve was weighed. Consolidation Detergent powder is enclosed in a commercially available detergent carton that does not contain a moisture barrier. The product of this invention is 22cm
2.6Kg in a box of (W) x 30.5cm (H) x 6.5cm (D)
For the control product, 2.6 kg was sealed in a 25.5 x 37.5 x 10 box. 4mm x 4 after standing at 30℃, 80%RH for 3 weeks
Powder was poured onto a sieve of 1.0 mm in diameter, and the weight A (Kg) of the powder remaining on the sieve and the weight B (g) passed through the sieve were measured, and the passage rate (C) was determined by the following formula. C (%)=B/A+B×100

【table】

Claims (1)

[Scope of Claims] 1 An unneutralized sulfonated product or/and a sulfated product (hereinafter referred to as an unneutralized product) is mixed with 2 to 10 mol of sodium carbonate and 1 to 10 mol of sodium carbonate per 1 mol of the unneutralized product. Neutralize and mix with water in a strong shearing device,
A method for producing an ultra-concentrated powder detergent, which is characterized by cooling to 40°C or less and then pulverizing or crushing and granulating it together with powdered zeolite and other detergent formulations. 2. The manufacturing method according to claim 1, wherein a detergent formulation such as sodium silicate, a high molecular weight organic polymer containing a carboxyl group and/or a hydroxyl group, and a cleaning aid are added during neutralization and mixing. 3 The unneutralized product has a linear or branched alkylbenzenesulfonic acid having an alkyl group having an average of 10 to 16 carbon atoms, an alkyl sulfate ester or an alkenyl group having an alkyl group having an average of 10 to 18 carbon atoms, and one molecule The method according to claim 1, wherein the alkenyl ether sulfate is an alkenyl ether sulfate to which an average of 0.5 to 8 moles of ethylene oxide or a mixed alkylene oxide of ethylene oxide and propylene oxide or butylene oxide is added.